Iron and iron metal containing alloys such as mild steel are well-known materials used in constructing the apparatus of aqueous systems in which system water circulates, contacts the iron based metal surface, and may be concentrated, such as by evaporation of a portion of the water from the system. Even though such metals are readily subject to corrosion in such environments, they are used over other metals due to their strength and availability.
It is known that various materials which are naturally or synthetically occurring in the aqueous systems, especially systems using water derived from natural resources such as seawater, rivers, lakes and the like, attack iron based metals (the term "iron based metals" shall mean in the present disclosure and the appended claims iron metal and metal alloys containing iron therein, i.e. ferrous metals). Typical devices in which the iron metal parts are subject to corrosion include evaporators, single and multi-pass heat exchangers, cooling towers, and associated equipment and the like. As the system water passes through or over the device, a portion of the system water evaporates causing a concentration of the dissolved materials contained in the system. These materials approach and reach a concentration at which they may cause severe pitting and corrosion which eventually requires replacement of the metal parts. Various corrosion inhibitors have been previously used.
Chromates and inorganic phosphates or polyphosphates have been used in the past to inhibit the corrosion of metals which is experienced when the metals are brought into contact with water. The chromates, though effective, are highly toxic and, consequently, present handling and disposal problems. Phosphates are non-toxic. However due to the limited solubility of calcium phosphate it is difficult to maintain adequate concentrations of phosphates in many instances. The polyphosphates are also relatively non-toxic, but tend to hydrolyze to form orthophosphate which in turn like phosphate itself can create scale and sludge problems in aqueous systems (e.g. by combining with calcium in the system to form calcium phosphate). Moreover, where there is concern over eutrophication of receiving waters, excess phosphate compounds can provide disposal problems as nutrient sources. Borates, nitrates, and nitrites have also been used for corrosion inhibition. These too can serve as nutrients in low concentrations, and/or represent potential health concerns at high concentrations.
In addition, environmental considerations have also recently increased concerns over the discharge of other metals such as zinc, which previously were considered acceptable for water treatment.
Much recent research has concerned development of organic corrosion inhibitors which can reduce reliance on the traditional inorganic inhibitors. Among the organic inhibitors successfully employed are numerous organic phosphonates. These compounds may generally be used without detrimentally interfering with other conventional water treatment additives.
Another serious problem in industrial water systems, especially in cooling water systems, industrial evaporators, and boilers is the deposition of scale, particularly scale-forming salts such as certain carbonates, hydroxides, silicates and sulfates of cations such as calcium and magnesium from aqueous solutions onto heat transfer surfaces. Much of water used in cooling water systems is supplied by the rivers, lakes, ponds, or the like and contains various amounts of scale-forming salts. In cooling tower systems, the cooling effect is achieved by evaporation of a portion of the circulating water in passing over the tower. Because of the evaporation which takes place in cooling, the solids in the water become concentrated. Moreover, because of the inverse solubility of calcium carbonate, calcium sulfate and other hardness salts, the problem of the formation of water-insoluble scales on the heat transfer surfaces is intensified.
Various organic phosphonates have been considered for use in scale control. For example, U.S. Pat. No. 3,336,221 describes a method of inhibiting the precipitation of scale-forming salts in an aqueous system comprising adding to said system amino tri (methylphosphonic acid) or phosphonomethyl ethanolamines. Unfortunately, these compounds are not chlorine resistant and degrade in the presence of free chlorine which commonly used as a disinfectant or biocide in many aqueous systems. U.S. Pat. No. 3,214,454 teaches use of certain acylation products of phosphorous acid (e.g. hydroxyethylidene diphosphonic acid) for scale control. Unfortunately various phosphonate including hydroxyethylidene diphosphonic acid and amino tri(methylphosphonic acid) are very sensitive to calcium hardness and prone to form calcium phosphonate precipitates.
U.S. Pat. No. 3,474,133 discloses that certain organo-phosphono-amine oxide compounds can be prepared by oxidizing organo-phosphono amine with a suitable oxidizing agent. For instance ethanol bis(dihydrogen phosphonomethyl) amine can be reacted with H.sub.2 O.sub.2 to yield ethanol bis(dihydrogen phosphonomethyl) amine oxide (i.e. HOCH.sub.2 CH.sub.2 (O) (CH.sub.2 PO.sub.3 H.sub.2).sub.2); and tris(dihydrogen phosphonomethyl) amine can be reacted with H.sub.2 O.sub.2 to yield tris(dihydrogen phosphonomethyl) amine oxide (i.e. ON(CH.sub.2 PO.sub.3 H.sub.2).sub.3). It is disclosed that the organo-phosphono amine oxides have utility in practically all fields of organic chemistry wherein their acidic or salt and/or amine oxide properties can be utilized; and the various utilities indicated for the compounds in such fields include utility as sequestering or chelating agents, water treating agents, stabilizers for peroxy compounds and corrosion inhibitors. In particular, the acids and water soluble salts of the tris(phosphono lower alkylidene) amine oxides are reported to exhibit the property of being effective sequestering agents for metal ions in alkaline mediums. For example, the penta sodium salt of tris(dihydrogen phosphonomethyl) amine oxide is reported to sequester calcium ions in alkaline media in over a mole per mole basis. These tri(phosphono lower alkylidene) amine oxide compounds are considered very sensitive to calcium hardness and they are prone to form calcium phosphonate precipitates.
There is a continuing need for safe and effective water treating agents which can be used to control corrosion or to control scale formation, particularly when substantial calcium is present in the system water. Water treating agents of this type are especially valuable if they remain stable in the presence of free chlorine which is commonly used in aqueous systems as a biocide or disinfectant.